Computational Study of the Reactivity of N-Phenylacetamides in the Alkaline Hydrolysis Reaction

Abstract

A number of molecular quantities were tested as reactivity indexes for the alkaline hydrolysis reaction of a series of 15 N-phenylacetamides para substituted in the aromatic ring. The Hammett σ constants and the shifts of carbonyl stretching mode frequencies correlate satisfactorily with the predicted Hartree−Frock (HF)/6-31+G(d) and density functional theory B3LYP/6-31+G(d,p) energy changes for the rate-determining stage of the reaction, namely, the addition of a hydroxide ion and formation of a tetrahedral intermediate. Natural bond orbital atomic charges at the carbonyl carbon atom, the site of the nucleophilic attack, also offer a satisfactory basis for discussing the reactivity of the carbonyl compounds studied. The electrophilicity index ω describes well the overall tendency of the changing reactivity of the studied compounds. A quantitative description of the reactivity of the studied amides in the reaction considered is provided by the theoretically estimated electrostatic potential at the carbony...